Polyamine production



United States Patent 3,414,623 POLYAMINE PRODUCTION William B. Hayes, Odessa, Tern, assignor to El Paso Products Company, Odessa, Tex., a corporation of Texas No Drawing. Filed Oct. 26, 1965, Ser. No. 505,244 11 Claims. (Cl. 260585) ABSTRACT OF THE DISCLOSURE Preparation of alpha,omega-alkylenediamines useful as intermediates in the production of nylon which comprises the sequential steps of (1) oxy-dehydro-halogenating a saturated aliphatic hydrocarbon having at least three carbon atoms by reaction with a hydrogen halide and an oxygen-containing gas at a temperature of about 900 to 1100 F. in the presence of a ferric halide catalyst to produce an allylic halide; (2) condensing said allylic halide with an olefin under pyrolysis conditions at a temperature of about 900 to 1100 F. for a time sufiicient to effect substantial condensation thereof whereby said allylic halide is converted to its corresponding biallylic derivative; (3) hydro-halogenating said biallylic derivative by reaction with an excess of hydrogen bromide at a temperature of about 20 C. to 40 C. to obtain the conresponding alpha,omega-dibromoalkane; and (4) subjecting said alpha,omega-dibromoalkane to ammonolysis by reaction with a molar excess of ammonia at a temperature of about 0 to 100 C. to obtain the corresponding alpha-omega-alkylenediamine.

This invention relates to the production of aliphatic diamines and more particularly to a new and improved process for the production of aliphatic diamines according to a multistep procedure well suited for industrial scale operations.

As is well known, the nylon industry has assumed a role of vast commercial importance due in large measure to the unique characteristics of polyamide-type resins which render them highly valuable for use in a Wide variety of commercial applications. The ever-increasing demand for nylon-type products has correspondingly initiated widespread commercial demand for the provision of feasible processes for the production of nylon intermediates and especially alkylenediamines. These latter materials are of course, basic to the preparation of the several grades of nylon, and accordingly, a large measure of industrial research effort has been directed to improved processes for their synthesis economically.

However, the processes heretofore customarily employed for production of alkylene polyamines have been uniformly characterized by disadvantages which detract considerably from their desirability for use in a commercial manner. By way of example of the more significant disadvantages encountered with prior processes, there may be mentioned in particular, the relatively low yield of desired diamine product which in many cases has been intolerable, the strong tendency for formation of undesirable byproducts, such as secondary and tertiary-amino compounds, the high cost of starting materials, catalysts, process equipment, and the like. Moreover, disadvantages have been encountered because of the stringent process conditions required to be observed for efficacious implementation, the extended reaction times required, the dithculties associated with product recovery and purification, and the like. As a result, the desired product amine is invariably obtainable in but limited quantities and at relatively high costs.

For example, many of the processes employed here- 3,414,623 Patented Dec. 3, 1968 tofore for alkylenediamine production have included, among others, as an essential manipulative step, the catalytic reduction of an olefin dinitrile to the corresponding diamine. Representative of the foregoing processes are those that involve seriatim, the formation of a dihaloalkene by dimerization of the correspondingly terminally unsaturated alkenyl halide, hydrogenation of the dihaloalkene to provide the dihaloalkane and treatment of the dihaloalkane with a metal cyanide to form the dinitrile intermediate. The latter material is then catalytically-reduced with hydrogen to produce the desired diamine. Significantly, processes of the foregoing type have been found to be subject to manifold disadvantages, such as those described hereinabove, including low product yield and byproduct formation. Perhaps the paramount disadvantage, however, is one which adheres in the process itself by virtue of the fact that the additional steps of dinitrile formation and the reduction thereof are necessarily involved. The increased economic burden imposed thereby can, as will be readily apparent, be so prohibitive in some instances that successful maintenance of competitive commercial advantages is severely lessened and often lost completely.

In efforts to overcome or mitigate the foregoing and related disadvantages, previous investigators have resorted to various remedial techniques, such as improvements in the above described process, while others have turned to substantially different procedures. However, regardless of the particular refinements and/ or alternative processes heretofore proposed, only limited commercial success has been thus far obtained with the result that considerable area for improvement yet remains.

Accordingly, one object of the present invention resides in the provision of a new and improved process for the preparation of aliphatic diamines wherein the difliculties heretofore encountered are eliminated or otherwise mitigated to at least a substantial degree.

A further object of the present invention resides in the provision of a new and improved multistep synthesis for the formation of valuable aliphatic diamines wherein excellent yields and conversions are obtained without the excessive formation of interfering side reactions so as to achieve an economically attractive integrated process.

The process of the instant invention affords several advantages not found in the prior art reactions enumerated hereinabove. The combination reaction of this invention provides an integrated system employing four simple process steps which do not require the use of expensive and cumbersome reaction equipment. Moreover, each of the steps provides a selective amount of the desired product in substantially pure form. Furthermore, the products formed in the reactions are easily susceptible of recovery and isolation for entry into the next step or recycle into the reaction system for continuous operation of the overall process.

Still other and related objects and advantages of the present invention will become apparent from the following description thereof.

The attainment of the foregoing and related objects is made possible in accordance with the present invention, which in its broader aspects includes the provision of a new and improved process for the production of alpha, omega-alkylenediamines which comprises, sequentially;

(1) The oXy-dehydr0-halogenation of a saturated aliphatic hydrocarbon having at least two carbon atoms with a hydrogen halide and an oxygen-containing gas to produce an allylic halide;

(2) Condensation of the allylic halide with an olefin to form an alpha,omega-alkadiene;

(3) Hydrobromination of the alkadiene to prepare the corresponding alpha,omega-dibromoalkane; and

(4) Ammonolysis of the dibromoalkane to yield the corresponding alkylene diprimary diamine product.

In accordance with the discovery forming the basis of the present invention, it has been found that strict adherence to each of the foregoing steps in the chronological sequence specified makes possible the obtention of diamine product in yields heretofore unobtainable. While there is a tendency for the formation of byproducts in the form of dimers and other higher molecular weight materials, the separation of these undesirable materials from the desired diamine by distillation or other means is much easier than with existing conventional processes. Additionally, a significantly outstanding advantage of the process of the invention resides in the utilization of mild reaction conditions which do not necessitate high pressure equipment (4,000 p.s.i.g. or higher) resulting in case of separation of impurities thus reflecting a favorable cost picture as compared to other commercial processes. The commercial implications of this particular feature are of primary importance from an economic standpoint alone, not to mention the added savings attributable to the fact that the product amine is obtained in exceptionally high yield. However, it must be emphasized that the results provided by the present invention depend critically on the observance of each of the above-indicated steps, which will be described in considerable detail in the discussion which follows.

In order to clearly describe the process of the present invention, each of the unit reactions critical thereto will be separately described in the discussion which follows.

OXY-DEHYDRO-HALOGENATION OF ALIPHATIC HYDROCARBONS TO PRODUCE OLEFINIC HALIDES The initial step of the process is one of oxy-dehydrohalogenation performed on a saturated aliphatic hydrocarbon having at least two carbon atoms. The process of oxy-dehydrohalogenation results in the simultaneous dehydrogenation and halogenation of the hydrocarbon to form an olefinic or allylic halide compound. This step of the process is based on the unexpected discovery that, under the novel reaction conditions and catalysts employed, dehydrogenation as well as oxyhalogenation occurs to yield the allylic halides. In analogous reactions conducted heretofore, only halogenation of the hydrocarbon occurred by reason of the reaction of the oxygen with the hydrogen halide in the presence of a Deacon catalyst (e.g. CuCl whereby elemental halogen is produced. Thus, the novel conditions and catalyst of the initial step of the invention permit the product of the desired allylic halides in a single step.

This step of the process is believed to proceed according to the following equation wherein R may be hydrogen, alkyl, aryl, aralkyl, alkaryl, etc., X is a halogen atom and n is zero or an integer.

The hydrocarbons employed as starting materials in this initial step comprise saturated aliphatic hydrocarbons having at least two carbon atoms. Particularly preferred hydrocarbons include those of the straight and branch-chained alkane series having about two to about twelve carbons, such as ethane, butane, pentane, hexane, heptane, octane, nonane, etc. It will be appreciated of course, that substituents other than carbon and hydrogen may be present therein so long as they are essentially non-reactive and do not deleteriously affect the reaction involved under the conditions employed in each of the unit reactions, i.e. oxy-dehydro-halogenation, condensation, hydrohalogenation and ammonolysis.

For purposes of illustration, the process of the present invention will be illustrated, specifically, with reference to n-butane as the starting hydrocarbon with the A corresponding production of 1-chloro-3-butene, 1,7-octadiene, 1,8-dibromooctane and 1,8-diamin0octane.

However, it will be understood that other hydrocarbons of the type defined may be similarly employed.

The hydrocarbon feed is reacted with an hydrogen halide and an oxygen-containing gas in a reactor maintained at a temperature of about 900 F. to 1100 F. and preferably around 1000 F. in the presence of a ferric chloride catalyst whereby the allylic halide is selectively formed by oxy-dehydro-halogenation.

The ratio of reactants employed in the oxy-dehydrohalogenation reaction is not necessarily a critical feature of the invention. In this regard the ratio of reactants can be varied from about stoichiornetric proportions to an excess of one or more of the reactants depending upon the result desired.

The hydrogen halide reactant may be any of the hydrogen halides including hydrogen chloride, hydrogen bromide, hydrogen iodide or hydrogen fluoride. The hydrogen halide is introduced as an anhydrous gas. Hydrogen chloride is the preferred reactant for this step of the process.

The oxygen reactant may be present as free or elemental oxygen or in admixture with inert diluents such as nitrogen. A particularly suitable form of the oxygen reactant comprises a stream of air as it is easily obtained and inexpensive. However, elemental oxygen is preferred.

A critical aspect of the initial step of the novel process of this invention resides in the catalyst employed. It has been found that a catalyst system embodying a ferric halide (e.g., chloride, bromide, etc.), on a suitable support or carrier is selective in the oxy-dehydro-halogenation reaction toward the production of the desired allylic halide. The catalyst is preferably prepared by impregnaiing an inert material having considerable surface area with a solution of the ferric halide. Various well known carriers may be employed such as Alundum, silica gel, kieselguhr, pumice and the like. A preferred catalyst is ferric chloride deposited on an Alundum carrier. It is also within the scope of the invention, and repre- Senting a specific embodiment thereof, to employ other ferric salts, such as ferric sulfate as catalysts in the process. When employing this technique, the ferric sulfate would be converted in situ to ferric chloride by action of the chlorine present in the reaction.

Another critical aspect of the initial step of the process resides in the temperatures employed in the reaction. It is essential that the temperature in the reactor be maintained above about 900 F. for the selective character of the process to be achieved. A preferred temperature range is about 900 F. to 1100 F. with a specially preferred range of about 1000 F. to 1050 F. Temperatures lower than those specified result in the dominant formation of the chlorinated hydrocarbons whereas higher temperatures result in extreme pyrolysis to produce cyclic products.

The pressure employed in the reaction may range from at or near atmospheric to about 200 to 300 p.s.i.g. depending of course on the other reaction conditions. This is an especially attractive commercial feature of the process, as it serves to decrease equipment size and lower operating costs.

In operation of this step of the process, the ferric chloride catalyst is charged to a reactor and the temperature elevated to that specified, viz, about 1000 F. Thereafter, the aliphatic hydrocarbon, hydrogen halide gas and oxygen are introduced into the reactor and conducted over the catalyst at about 900 F. to 1100 F. The reactants are maintained at the specified temperature range for a period sufiicient for the reaction to go to completion and therefore contact periods will vary. However, it has been found that a residence time of about 0.1 to 5 seconds constitutes an adequate contact time with an especially preferred period of about 0.1 to 1 second.

The oxy-dehydro-halogenation step employing the ferric halide catalyst may be carried out by means of a fluidized bed, a moving bed reactor, a fixed bed reactor or an empty tube reactor as desired. A particularly suitable reactor is one employing the fiuidized bed technique as the ferric halide catalyst is volatile at the process reaction temperatures. In this apparatus the feed gases are passed through a fluidized bed of the catalyst. In the course of the reaction, the ferric halide (e.g., FeCl is removed from the bed and exits with the efiiuent gases. After leaving the reactor, the gases are first passed through a partial condenser where a water solution of the catalyst is recovered and subsequently sprayed back onto the hot support particles. The water quickly evaporates leaving a preponderance of the catalyst on the support.

A moving bed reactor may also be employed wherein the ferric halide particles are continuously circulated using an air-lift principle. At the top of the lift, after the lift air has been separated from the support particles, the recycle aqueous ferric halide is sprayed on the support. This method not only serves to keep the correct amount of ferric halide in the reactor, but also can be used as an effective method of temperature control by merely adjusting the amount of recycle water.

The components may be premixed before they are added to the reaction zone or they may be added separately. To insure a thorough intimate mixing of the components, however, it is generally desirable to premix prior to introduction into the reaction zone. It is also advantageous in most instances to preheat the components, either separately or in admixture to a temperature below the operating temperature before they are added to the reaction zone.

The products emitted from the reactor comprise a major proportion of allylic halide with minor amounts of olefinic hydrocarbons, saturated hydrocarbons, halogenated hydrocarbons and hydrogen halide. The allylic halide products and byproducts may be recovered by any suitable means such as fractional distillation, extraction and the like.

The desired allylic halide recovered from the catalytic reactor is then passed, together with the halogenated hydrocarbon, to the second reactor for the condensation reaction as delineated hereinafter. Any olefinic hydrocarbons or unreacted starting material may be recycled to the initial step after separation from the hydrogen halide.

The following examples illustrate the results obtained when proceeding according to the above-described method.

Example: 1

The reactor employed in this experiment comprised a Vycor tube having a 19 mm. inside diameter and 1030 mm. in length, with a 6 mm. outside diameter thermowell down the center. The empty volume of the reactor was packed with a catalyst consisting of ferric chloride impregnated on Alundum. The reactor was inserted into a cylindrical -bronze aluminum block mounted inside an electrical heater.

The catalyst charged to the reactor was prepared by saturating Alundum with an aqueous solution of ferric chloride (9.1 weight percent FeCl -6H O), draining the excess liquid and drying the impregnated Alundum in an oven at 400 F.

n-Butane at a rate of 0.80 gm. per minute, hydrogen chloride at a rate of 0.65 gm. per minute, oxygen at a rate of 0.30 gm. per minute were then passed through rotameters into the head of the reactor where they were mixed and then forwarded into the reactor proper. The temperature of the bronze-aluminum block was maintained at 1006 F. and the maximum temperature of the catalyst bed was 1077 F. at a bed depth of 15 inches. The residence time was 0.2 second.

Samples of the efiluent gas were collected and analyzed by means of gas chromatography. It was found that about 52% of the butane was converted to products. Of the butane that was converted, 69% went to form butylene which could be recycled to be chlorinated, 12.1% went to form 1-chloro-3-butene and 1.7% went to form 1,7- octene. The n-butane starting material recovered could also be recycled. The 1-chloro-3-butene product and diolefin product are passed to the condensation step.

Example 2 This example is the same as Example 1 except that ferric sulfate was employed as the catalyst rather than ferric chloride. The catalyst was prepared as in Example 1. When the catalyst was employed in the reaction, the ferric sulfate was converted in situ to the chloride. The flow conditions and reactants were the same as in the previous example as was the reactor. In this example, the block temperature was 1009 F. and the maximum temperature of the catalyst bed was 1075 F. at a bed depth of 16 inches.

Analyses of the reactor efiluent yielded the following results. Approximately 52% of the n-butane was converted to products of the starting material converted, 61% went to form 1-butene, and 11.1% went to form l-chloro- 3-butene. Of the HCl converted, 50% went to form 1- chloro-3-butene.

The 1-chloro-3-butene and chlorinated butane recovered from this step are then forwarded to the second or condensation step of the process.

CONDENSATION OF ALLYLIC HALIDE WITH OLEFINS TO PRODUCE DIOLEFINS The allylic halides employed in this step of the process refer to those compounds produced in the initial step described hereinabove. For purposes of illustration, and in conformance with the first step described hereinabove, the starting olefin or allylic halide will be 1-chloro-3 butene. However, it will be understood that other allylic halides of the type described hereinabove may be similarly employed.

A number of methods have been provided by which allylic compounds may be converted to their nonconjugated polyunsaturated derivatives including, for example, simple condensation of the allylic halide in the presence of silver or copper, the latter being provided in either supported or powdered form. Also, dehydrohalogenation of the corresponding halogen substituted derivative has been attempted. However, the foregoing and related methods have proven unsatisfactory, particularly for large scale operations since the yields obtained are in many instances low and reactants are expensive.

In accordance with the present invention and pursuant to the maximum attainment of the improvements thereof, it is required that conversion of the allylic halide to preferably an alpha,omega-d iolefin be efiected via a pyrolysis technique. According to this step of the process, the allylic halide, e.g., 1-chloro-3-butene, is heated above about 900 F. for a short period of time in the presence of an excess of an organic compound containing a replaceable hydrogen atom, whereby the diolefin-forming reaction proceeds to substantial completion. The desired diolefin derivative may thereafter be readily recovered from the resulting mixture. The replaceable hydrogen-containing compounds suitable for use herein for reaction with the allylic halide are in general organic compounds having at least one replaceable hydrogen atom and which are stable in the presence of the hydrogen halide evolved at the elevated reaction temperatures employed. As particular examples of such compounds there may be mentioned the olefin series such as l-butene, l-pentene, l-hexene, l-heptene, l-octene and the like.

The relative proportions of the respective components should be such as to yield a mixture comprising the ganic compound and allylic halide in molar ratios varyatom in excess of the halide and preferable in a molar excess of at least 3 to 1. Optimum results are achieved, for example, when employing the hydrogen-containing or- L test meter to obtain their volume. Samples of the offgases were analyzed chromatographically and the contents of the cold traps were combined and analyzed.

The results obtained are itemized in Table I herein-- below.

TABLE L-CONDENSATION OF l-CHLORO-i-BUTENE WITH l-BUIENE Selectivity 1 Selectivity 2 Ex. 1-butene, 1-chl0ro-3- Reactor pressure, Maximum tem- Conversion 1- I-chloro-3- 1-chl0r0-3- N0. gIIlS./H1l]1. butene, p.s.i.g. perature, F. c loro-3- butene to 1.7 butene, 1,7- gms/min. butene octadiene, octadiene,

percent percent 1 Selectivity based on material balance to determine 1-chl0ro3-buten e disappearance. 2 Selectivity based on HC-l recovery to determine 1-chloro'3'butene disappearance.

The temperature employed for the pyrolysis reaction should in general range from about 850 F. to about 1100 F. The particular temperature employed in each case will depend, inter alia, on the nature of the starting materials, the residence period, etc. With 1-chloro-3-butene, preferred temperatures generally range 900 F. to 1050 F. and more preferably from about 1000 F. to about 1050 F.

The pressure employed in the reaction zone may likewise vary over a wide range, i.e., from subatmospheric to superatmospheric as desired. However, the most effective pressure found conducive for convenience of process operation with respect to recycling of unreacted starting materials has been found to be about 50 to 300 p.s.1.g.

The residence period required for substantial completion of the reaction will depend, inter alia, on the desired degree of conversion of unsaturated halide, which in turn depends on the temperature and nature of the halide. For the aliphatic halides, such as 1-chloro-3-butene, it has been found that the desired conversion per pass can be obtained in periods ranging from 0.1 to 50 seconds at temperature of about 900 F. to 1100 F. In general, the utilization of higher temperatures will result in decreased residence times.

The components may be premixed prior to entry into the pyrolysis zone or they may be added separately. In general, however, and to insure thorough mixing, it is preferable to premix the components. It is also generally advantageous to preheat the components separately or in admixture, to a temperature below the operating temperature prior to entry into the reaction zone.

After reaction, the mixture withdrawn from the reaction zone is cooled, condensed and scrubbed or otherwise treated to remove the hydrogen chloride formed in the reaction. The diolefins may then be recovered by any suitable means such as fractional distillation, extraction, etc. Any allylic halide or organic compound containing replaceable hydrogen which are recovered may likewise be conveniently recovered by conventional means or recycled to the reaction.

The following examples illustrate in tabular form the results obtained when proceeding according to the abovedescribed method. The pyrolysis reactor comprised a stainless steel tube inserted in an electrical heater having an inside diameter of one inch and having a one-fourth inch outside diameter thermowell inserted down the center thereof. The tube was forty-three inches long.

The procedure employed was as follows: the l-chloro- 3-butene was pumped and the butene was passed through a rotameter with mixing occurring in the head of the reactor for entry into the reactor proper. The off gases evolved were directed through a series of Dry Ice-acetone traps maintained at about 78 C. Any gases not condensed at this temperature were passed through a wet HYDROMINATION OF THE DIOLEFIN Hydromination of the diolefins obtained from step two is readily achieved by use of a low temperature directional addition of hydrogen bromide.

The procedure by which the HBr is added to the diolefins is accomplished in accordance with the present invention by the employment of reaction initiators comprising peroxides or hydroperoxides and/ or materials which yield peroxides or hydroperoxides under the reaction conditions employed.

The hydrobromination reaction proceeds via abnormal addition, i.e., in a manner contrary to that prescribed by the Markownikotf rule. As is well known, the latter rule sets forth the proposition that if an unsymmetrical hydrocarbon combines with a halogen acid, the halogen adds to the carbon atom having the fewer hydrogen atoms. A hydrocarbon is unsymmetrical within the meaning of the rule if the unsaturated linkage divides the compound into two dissimilar groups. Accordingly, abnormal addition is descriptive of the condition whereby hydrogen and halogen atoms are added in positions which are interchanged with respect to the mechanism of addition prescribed by the Markownikolf rule.

According to the present invention, it has been found that if the hereindescribed reaction initiators are added to the diolefins produced by the condensation of step two and hydrogen bromide is added thereto under the reaction conditions set forth herein, that abnormal addition of the HBr occurs selectively yielding an alpha, omega dibromoalkane.

Without intending to be bound by any theory, it is postulated, that the reaction mechanism involved in the hydrobromination reaction is free-radical in nature and can be described according to the following series of reactions:

The R. in the first equation represents a free radical generated as the result of either a peroxide, hydroperoxide and/or a material which yields peroxides or hydroperoxides under the conditions of the reaction.

The free radical induced hydrobromination reaction employed in the method of the present invention is effectively carried out using any of the well known freeradical initiators. However, superior results are achieved when employing oxygen in uncombined form, i.e., air or oxygen, since each of these materials exhibits a ready tendency to form peroxides or hydroperoxides under the conditions employed in the reaction. It is to be noted, however, that excellent results are also obtainable by the use of materials wherein the oxygen is present in combined form, i.e., peroxides and hydroperoxides. As examples of these latter materials there may be mentioned the dialkyl peroxides, the alkyl hydrogen peroxides, the diacyl peroxides and the like. Also inorganic peroxides may be employed to advantage in their free and salt form. Optimum results, however, have been realized by the generation of peroxides in situ by passage of uncombined oxygen through the diolefin during hydrobromination and this represents a preferred embodiment of this step of the inventive method.

The hydrobromination reaction is conducted by dissolving the free-radical generating compound in the diolefin in the liquid phase as an oxygen-containing gas was bubbled therethrough. Thereafter, the resultant mixture was contacted with gaseous hydrogen bromide employing the conditions set forth hereinafter.

The diolefin reactant subjected to hydrobromination in this step of the process comprises those dienes produced in the condensation step set forth hereinabove. For purposes of illustration, this step of the method will be described with respect to the hydrobromination of 1,7-octadiene to selectively produce 1,8-dibromooctane.

The diene recovered from the condensation step is purified and then hydrobrominated at low temperatures. The reaction is conducted by introducing the free-radical generator into the diolefin and then adding the hydrogen bromide.

The amount of free radical initiator employed is not particularly critical, aside from the obvious requirement that it be sufiicient to permit the desired reaction rate. This can readily be accomplished by the use of exceedingly small amounts and especially so when operating under the preferred conditions since the reaction, once initiated, is substantially self-sustaining. In general,.however, the amount of oxygen initiator employed should be such as to yield a peroxide or hydroperoxide concentration in the reaction mixture of about 3.0 mole percent. The initiator may be introduced into the liquid diolefin by any suitable method. However, it has been found that the gaseous oxygen-containing gas can be readily introduced into the diolefin by merely bubbling the same thereinto. This may be accomplished by use of a capillary tube.

The proportion of hydrogen bromide employed in the reaction should be maintained within the prescribed limits in order to assure the realization of advantageous results. In general, the hydrogen bromide should be employed in a stoichiometric excess of about 150 percent based on flow rate. This excess HBr corresponds to a range of about 1.5 to 3.5 parts HBr to 1 part diolefin by moles.

The temperatures employed in this step of the process are generally in the range of about --20 C. to 40 C. although variations may occur depending on the diolefin reactant. In general, it is necessary to employ reaction temperatures slightly lower than ambient temperature. A preferred reaction temperature for realization of advantageous results is about 30 C. The pressure employed may range from subatmospheric to superatrnospheric depending on the reactants and temperature employed. However, atmospheric temperatures are employed in the preferred embodiment.

It has been found that improved conversion and selectivity values are particularly manifest when the diolefin and initiator are premixed prior to introduction of the hydrogen bromide. Accordingly, this procedure also represents a preferred embodiment in carrying out the inventive process.

It is deemed essential that the hydrobromination reaction be conducted in an atmosphere free from moisture as the presence of the same has been found to be deleterious to formation of the desired products. To achieve the desired moisture absence, it may be necessary to initially dry the reaction zone as by heating and then maintaining an inert atmosphere therein such as by use of a stream of nitrogen or other conventional means.

Example 14 The reactor employed in this example comprised a coiled glass tube having an inside diameter of 6 mm. and a volume 'of 30 cc. The coil was enclosed in a glass jacket which served to control the reaction temperature by the use of cooling water. The cooling water was -main tained at about 30 C.

The 1,7-octadiene was pumped at a rate of 0.240 grammole per hour and admixed with 0.114 gram-mole per hour of oxygen. This stream of diene and oxygen was then mixed with 0.604 gram-mole per hour of gaseous hydrogen bromide and sent directly to the reactor.

At the conclusion of the reaction, the reactor effluent was trapped in an ice-colled receiver and a sample thereof analyzed by gas chromatography. The analytical results are shown below in Table -II.

As may be observed from the above analyses, the hydrobromination reaction is decidedly selective toward anti-Markownikoff addition to produce the 1,8-dibrom-ooctane derivative in a predominant amount. Also, it may be seen that the conversion to brominated compounds is nearly Separation of the dibrominated compounds is exceedingly difficult, but under the novel method of this invention, it has' been found to be necessary by resort to the final step of the invention, the amination reaction which is described hereinafter.

AMMONOLYSIS OF THE HYDROBROMINATED DIOLEFIN The mixture of dibrominated compounds is next sent to the amination and final step of the process for reaction with ammonia under closely controlled conditions as described hereinafter.

It is well known, that alkyl halides can be converted directly to their corresponding amine derivatives by treatment with ammonia. However, the methods heretofore provided for effecting such conversions have required the use of elevated temperatures on the order of 100 C. and often in excess of 200 C. These elevated tem perature conditions have been found to result in commercially feasible reaction rates, product yield, etc. However, the products derived from these prior processes have gneerally been composed of a mixture of various monoand polyamines and high molecular weight materials which are difficultly separable. It has been necessary that resort be made to further treatment, e.g., fractional distillation, extraction and the like in order to eventually separate and isolate the desired products. Furthermore, the use of the elevated temperatures frequently give rise to excessive amounts of undesirable byproducts.

Contrary to the prior processes described above, the amine-forming reaction contemplated for use herein is carried out under relatively mild temperature conditions employing specific proportions of the ammonia reactant. The. reaction is also carried out under slight conditions of pressure.

The ammonolysis reaction is performed in the presence of an excess of anhydrous ammonia, the latter being employed in the liquid phase. The ammonia reactant is employed in a large molar excess on the order of about 50 to 300:1, a ratio which has been found to result in selective production of the desired diamino product. This result is somewhat surprising as it would ordinarily be expected that the ammonia and dibromo compound would react to form high molecular weight derivatives of the resinous variety. However, when operating under the conditions hereinafter specified, it has been found that any tendency for production of such products is substantially eliminated.

As pointed out hereinabove, the ammonolysis reaction has been found to result in higher selectivities of desired product when employing a large excess of the anhydrous ammonia. A particularly preferred ratio has been found to be about 50 to 300 moles of ammonia per mole of dibrominated hydrocarbon.

The dihalogenated hydrocarbon to be aminated in this step of the process may be any desired dihalogenated product but preferably is the dibrominated derivative produced in the preceding step. For purposes of illustration and in conformance with the overall multistep process described herein, the amination will be described with respect to the use of 1,8-dibrornooctane as produced in the next preceding step.

A truly advantageous feature of the present invention, and one on which novelty is predicated, is that the mixture of dibrominated derivatives obtained from the previous step may be aminated without the intermediate isolation of the alpha,omega-dibrominated hydrocarbon. It has been found that the mixture of dibrominated products may be directly subjected to amination with surprising results. This unexpected benefit is that amination, under the conditions specified herein, converts the dibromo com pounds, other than the 1,8-dibromooctane, etc., into cyclic amines which may be easily separated from the desired 1,8-diaminooctane. Ease of product separation at this stage of the process results in great economic benefits, particularly when operating on a large-scale.

A further advantage of the instant step is that an acidic material, such as an ammonium halide is not necessary to attain the objects of the invention. This is in contradistinction to prior processes wherein the presence of an acidic material, such as ammonium chloride, was thought necessary to prevent excessive byproduct formation.

The amination process of this invention is carried out under mild conditions of temperature as specified herein above. The reaction temperature lies in the range of about to 100 C., and preferably about to 50 C. An especially preferred reaction temperature is about 30 C.

At these temperatures, it has been found that the pressure of the reaction should be maintained at about 100 to 1000 p.s.i.g. depending on the temperature employed. A preferred pressure operation is about 100 to 500 p.s.i.g. with an especially preferred reaction pressure of about 200 p.s.i.g. Hence, another advantage of the process is realized by obviating the need for expensive high pressure operating equipment.

The reaction ordinarily requires from about ten minutes to about five hours to go to completion depending on the starting materials employed. However, the reaction is preferably conducted by mixing the reactants in a relatively short period, such as fifteen to twenty minutes and thereafter agitating until the reaction is completed.

The reaction is conducted by charging the anhydrous liquid ammonia to a stirred autoclave and adding the di brominated compound thereto over a short period. After completion of the reaction, and removal of the excess ammonia, the resulting aminated mixture is neutralized with caustic to free the amine from its hydrogen bromide salt. Thereafter, the hydrocarbon component of the effiuent is separated and sent to a conventional distillation train for purification of the diamine. The excess ammonia reactant is recycled in the continuous process and the alkali metal bromide is recovered for processing.

The alkali metal bromide (e.g., NaBr) is processed by reacting with chlorine to yield free bromine and sodium chloride. The bromine is recovered and hydrogenated to hydrogen bromide using a platinum catalyst. The HBr formed is thus suitably processed and recycled to the hydrobromination step.

The following example illustrates the application of the novel amination reaction of this invention as applied to the amination of 1,8-dibromooctane to produce octamethylenediamine. However, the example is to be considered solely as illustrative of the invention and not limiting thereon.

Example 15 The reactor employed in this example comprised a 1- liter stainless steel autoclave with agitation provided by a Magne Dash stirrer.

19.4 gram-moles of anhydrous liquid ammonia were charged to the autoclave and the stirring commenced. Then, 0.065 gram-mole of 1,8-dibromooctane were added over a period of about 25 minutes. Thereafter, the reactor was stirred for four hours at a temperature of about 30 C. and a pressure of about 200 p.s.i.g. The material amounts added represent a ratio of 300 moles of ammonia to 1 mole of 1,8-dibromooctane.

At the conclusion on the reaction, the reactor contents were discharged into a flask containing ml. of methanol and the free ammonia was allowed to weather off. The residue was then treated with 16 grams of NaOCH dissolved in 60 ml. of methanol. This mixture was sampled and analyzed by means of gas chromatography and the results thereof are appended in Table III below.

Product Percent efficiency Octztniethyleneimine Octamethylenediamine ()ther dimers Cyclic dimers Linear dimers Although the present invention has been specifically set forth in connection with the preparation of octamethylenediamine, it will be understood that the process described herein is generally applicable to the production of alkylene diamines from starting hydrocarbons of the type defined herein. For example, the present invention is likewise eminently suitable for the preparation of mixtures of alkylene diamines which, of course, could be readily achieved by merely employing two or more different hydrocarbons as starting materials or employing different olefins in the condensation step.

The invention has been described with respect to certain preferred embodiments thereof, and there will become obvious to persons skilled in the art other variations, modifications and equivalents which are to be understood as coming within the scope of the present invention.

What is claimed is:

1. A process for the production of alpha,omega-alkylenediamines which comprises the sequential steps of: (l) oxy-dehydro-halogenating an alkane having about two to about twelve carbon atoms by reaction of said alkane with hydrogen halide and an oxygen-containing gas at a temperature of 900 to 1100 F. in the presence of a ferric halide catalyst to produce an allylic halide; (2) condensing said allylic halide with a monoolefin hav ing up to eight carbon atoms under pyrolysis conditions at a temperature of about 850 to 1100 F. :to produce the corresponding diallylic derivative; (3) hydrobrominating said diallylic derivative by reaction with an excess of hydrogen bromide in the presence of a peroxide or hydroperoxide free radical initiator at a temperature of 20 to 40 C. to obtain the corersponding alpha,omegadibrominated alkane, and (4) subjecting said alpha,omegadibrominated alkane to ammonolysis by reaction with a molar excess of anhydrous liquid ammonia at a temperature of about 10 to 50 C. and a pressure of 100 to 13 1000 p.s.i.g. and recovering the alpha,omega-alkylenediamines produced.

2. A process according to claim 1 wherein the hydrogen halide reactant in (l) is hydrogen chloride.

3. A process according to claim 2 wherein the ferric halide catalyst in (1) is ferric chloride on a carrier.

4. A process according to claim 3 wherein the reaction is conducted at a temperature of about 1000 to 1050 F. at atmospheric pressure.

5. A process according to claim 1 wherein condensation step (2) is conducted at a pressure of about 50 to 300 p.s.i.g.

6. A process according to claim 5 wherein the condensation reaction is conducted for a residence time of about 0.1 to 50 seconds.

7. A process according to claim 1 wherein hydrobromination step (3) is carried out employing about a 150% stoichiometric excess of hydrogen bromide.

8. A process according to claim 7 wherein the peroxide or hydroperoxide free-radical initiator is selected from the group consisting of peroxides, hydroperoxides and substances which yield peroxides or hydroperoxides under the conditions of the reaction.

9. A process according to claim 8 wherein the diallylic derivative and initiator are premixed prior to introduction of the hydrogen bromide.

10'. A process according to claim 1 wherein the ammonolysis step (3) is conducted employing an excess of 50 to 300 moles of ammonia per mole of dibrominated alkane.

11. A process according to claim 10 wherein the ammonolysis reaction is conducted at a temperature of about C. and a pressure of about 200 p.s.i.g.

References Cited UNITED STATES PATENTS 2,550,020 4/1951 OXley et al. 260585 3,052,735 9/1960 Hodgson ct al 260680 X 3,304,337 2/1967 Jordan et a1 260-654 X OTHER REFERENCES Groggins: Unit Process in Organic Synthesis, McGraw- Hill, New York (1947), page 228.

CHARLES B. PARKER, Primary Examiner.

R. L. RAYMOND, Assistant Examiner. 

